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In the title compound, C24H18O4S3, the central S atom lies on a twofold axis. The asymmetric unit, one half of the mol­ecule, is almost planar, with a dihedral angle between the phenyl and thienyl rings of 10.9 (1)°. The C1-S1-C1' angle is 103.5 (1)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013034/cv6050sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013034/cv6050Isup2.hkl
Contains datablock I

CCDC reference: 157877

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.053
  • wR factor = 0.150
  • Data-to-parameter ratio = 18.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Supramolecular chemistry based on molecular recognition has added a new dimension to chemistry and stereochemistry and is a fast growing subject. Considered efforts generally directed towards modeling for biological non-covalent binding in chemical systems resulted not only in the synthesis of numerous artificial receptors but also in the development of innovative approaches to the generation of selective non-covalent binders (Haldar et al., 1997). Ray et al. (2001) have prepared the title compound, (I), by a very recently method developed for the synthesis of sulfur pivoted cavity-shaped polycyclic thiophene derivatives in three steps from diphenyl sulfide. We have undertaken an X-ray structure determination of (I) in order to establish its chemical structure and conformation.

In the compound (I), the bond lengths and angles show normal values. The values of the phenylthiophene moiety agree with those observed in the related structure previuously studied (Joseph et al., 1991). The C1—S1—C1' angle is 103.5 (1)°.

In the structure (I), there is only one half of the molecule in the asymmetric unit, and the unit-cell volume contains four molecules. One half of the molecule is related to the other by a twofold axis passing through the S1 atom. One half of the molecule is nearly planar. Both the phenyl and thienyl rings are planar, with maximum deviations of 0.009 (3) Å at C3 and 0.009 (2) Å at C7. The mean planes through the phenyl and thienyl rings form a dihedral angle of 10.9 (1)°. The carbomethoxy group is also planar and is twisted by 8.4 (1)° from the plane of the thienyl ring.

Experimental top

The title compound, (I), was synthesized from commercially available diphenyl sulfide (Aldrich) by Friedel–Crafts acylation with excess of acetyl chloride and anhydrous aluminium chloride followed by the formation of bis-chloroaldehyde (phosphorustrichloride and dimethylformamide) and its condensation with two equivalents of methyl thioglycolate/triethylamine, and concomitant ring closure with 50% potasium hydroxide. Single crystals suitable for X-ray structure determination were obtained by slow evaporation from a benzene solution.

Refinement top

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids with the atom-numbering scheme.
4,4'-Bis(5-Carbomethoxy-2-thienyl)phenyl sulfide top
Crystal data top
C24H18O4S3F(000) = 968
Mr = 466.56Dx = 1.459 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 11.8692 (3) ÅCell parameters from 4461 reflections
b = 6.0255 (2) Åθ = 1.4–28.5°
c = 29.7783 (6) ŵ = 0.38 mm1
β = 94.221 (1)°T = 293 K
V = 2123.9 (1) Å3Prism, yellow
Z = 40.48 × 0.44 × 0.18 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
2620 independent reflections
Radiation source: fine-focus sealed tube1895 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
Detector resolution: 8.33 pixels mm-1θmax = 28.6°, θmin = 1.4°
ω scansh = 1315
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 78
Tmin = 0.839, Tmax = 0.935l = 3639
7327 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0803P)2]
where P = (Fo2 + 2Fc2)/3
2620 reflections(Δ/σ)max < 0.001
142 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C24H18O4S3V = 2123.9 (1) Å3
Mr = 466.56Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.8692 (3) ŵ = 0.38 mm1
b = 6.0255 (2) ÅT = 293 K
c = 29.7783 (6) Å0.48 × 0.44 × 0.18 mm
β = 94.221 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
2620 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1895 reflections with I > 2σ(I)
Tmin = 0.839, Tmax = 0.935Rint = 0.062
7327 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
2620 reflectionsΔρmin = 0.32 e Å3
142 parameters
Special details top

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based

on F, with F set to zero for negative F2. The threshold expression of

F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.00000.16957 (14)0.75000.0505 (3)
S20.40061 (5)0.32091 (10)0.61642 (2)0.0497 (2)
O10.52659 (15)0.7968 (3)0.54722 (6)0.0589 (5)
O20.58680 (18)0.4490 (4)0.55765 (8)0.0805 (7)
C10.08103 (18)0.0117 (4)0.71879 (7)0.0416 (5)
C20.0359 (2)0.2012 (4)0.69829 (10)0.0587 (7)
H2A0.03820.24170.70250.070*
C30.0995 (2)0.3296 (4)0.67184 (9)0.0569 (7)
H3A0.06830.45850.65900.068*
C40.20864 (18)0.2725 (3)0.66372 (7)0.0385 (5)
C50.25295 (19)0.0836 (4)0.68444 (8)0.0461 (5)
H5A0.32680.04250.68000.055*
C60.19001 (19)0.0460 (4)0.71161 (8)0.0458 (5)
H6A0.22170.17290.72510.055*
C70.27439 (18)0.4104 (4)0.63471 (7)0.0405 (5)
C80.2482 (2)0.6151 (4)0.61736 (8)0.0493 (6)
H8A0.18230.69030.62290.059*
C90.3288 (2)0.7012 (4)0.59064 (9)0.0497 (6)
H9A0.32270.83930.57670.060*
C100.4173 (2)0.5621 (4)0.58709 (7)0.0442 (5)
C110.51936 (19)0.5915 (4)0.56306 (8)0.0489 (6)
C120.6210 (2)0.8446 (5)0.52157 (10)0.0701 (8)
H12C0.63151.00230.52010.105*
H12A0.60700.78630.49170.105*
H12B0.68770.77720.53570.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0509 (5)0.0421 (5)0.0608 (5)0.0000.0193 (4)0.000
S20.0499 (4)0.0426 (3)0.0583 (4)0.0110 (3)0.0151 (3)0.0122 (3)
O10.0563 (10)0.0586 (11)0.0640 (11)0.0020 (8)0.0192 (8)0.0193 (9)
O20.0664 (12)0.0698 (14)0.1097 (17)0.0223 (11)0.0358 (11)0.0218 (12)
C10.0420 (11)0.0423 (12)0.0410 (11)0.0004 (9)0.0064 (8)0.0026 (9)
C20.0395 (12)0.0599 (16)0.0779 (18)0.0120 (11)0.0118 (11)0.0180 (13)
C30.0496 (14)0.0512 (14)0.0712 (17)0.0138 (11)0.0126 (12)0.0208 (12)
C40.0438 (11)0.0354 (11)0.0367 (11)0.0024 (9)0.0052 (8)0.0023 (8)
C50.0439 (12)0.0444 (13)0.0515 (13)0.0097 (10)0.0130 (9)0.0036 (10)
C60.0492 (13)0.0390 (12)0.0504 (13)0.0085 (10)0.0114 (10)0.0058 (10)
C70.0454 (11)0.0378 (11)0.0389 (11)0.0034 (9)0.0063 (8)0.0023 (9)
C80.0509 (13)0.0409 (12)0.0570 (14)0.0106 (10)0.0111 (10)0.0042 (10)
C90.0564 (14)0.0365 (12)0.0567 (14)0.0056 (10)0.0084 (11)0.0055 (10)
C100.0514 (13)0.0377 (12)0.0441 (12)0.0022 (10)0.0074 (9)0.0035 (9)
C110.0475 (13)0.0513 (14)0.0485 (13)0.0027 (11)0.0079 (10)0.0073 (11)
C120.0578 (16)0.089 (2)0.0649 (18)0.0105 (15)0.0165 (13)0.0180 (15)
Geometric parameters (Å, º) top
S1—C11.765 (2)C4—C71.464 (3)
S1—C1i1.765 (2)C5—C61.382 (3)
S2—C101.715 (2)C5—H5A0.9300
S2—C71.718 (2)C6—H6A0.9300
O1—C111.329 (3)C7—C81.364 (3)
O1—C121.431 (3)C8—C91.389 (3)
O2—C111.193 (3)C8—H8A0.9300
C1—C61.371 (3)C9—C101.354 (3)
C1—C21.384 (3)C9—H9A0.9300
C2—C31.370 (3)C10—C111.462 (3)
C2—H2A0.9300C12—H12C0.9600
C3—C41.379 (3)C12—H12A0.9600
C3—H3A0.9300C12—H12B0.9600
C4—C51.380 (3)
C1—S1—C1i103.51 (14)C8—C7—C4128.3 (2)
C10—S2—C791.82 (11)C8—C7—S2110.07 (17)
C11—O1—C12116.8 (2)C4—C7—S2121.60 (16)
C6—C1—C2118.7 (2)C7—C8—C9114.1 (2)
C6—C1—S1118.83 (17)C7—C8—H8A123.0
C2—C1—S1122.31 (17)C9—C8—H8A123.0
C3—C2—C1120.5 (2)C10—C9—C8112.6 (2)
C3—C2—H2A119.8C10—C9—H9A123.7
C1—C2—H2A119.8C8—C9—H9A123.7
C2—C3—C4121.6 (2)C9—C10—C11129.7 (2)
C2—C3—H3A119.2C9—C10—S2111.44 (18)
C4—C3—H3A119.2C11—C10—S2118.88 (18)
C3—C4—C5117.4 (2)O2—C11—O1124.1 (2)
C3—C4—C7120.7 (2)O2—C11—C10124.5 (2)
C5—C4—C7121.96 (19)O1—C11—C10111.4 (2)
C4—C5—C6121.5 (2)O1—C12—H12C109.5
C4—C5—H5A119.2O1—C12—H12A109.5
C6—C5—H5A119.2H12C—C12—H12A109.5
C1—C6—C5120.3 (2)O1—C12—H12B109.5
C1—C6—H6A119.8H12C—C12—H12B109.5
C5—C6—H6A119.8H12A—C12—H12B109.5
C1i—S1—C1—C6143.3 (2)C10—S2—C7—C81.38 (19)
C1i—S1—C1—C241.89 (19)C10—S2—C7—C4179.85 (19)
C6—C1—C2—C30.8 (4)C4—C7—C8—C9179.6 (2)
S1—C1—C2—C3175.6 (2)S2—C7—C8—C91.3 (3)
C1—C2—C3—C41.8 (4)C7—C8—C9—C100.4 (3)
C2—C3—C4—C51.9 (4)C8—C9—C10—C11178.8 (2)
C2—C3—C4—C7178.9 (2)C8—C9—C10—S20.7 (3)
C3—C4—C5—C61.2 (4)C7—S2—C10—C91.2 (2)
C7—C4—C5—C6179.7 (2)C7—S2—C10—C11178.4 (2)
C2—C1—C6—C50.1 (4)C12—O1—C11—O21.0 (4)
S1—C1—C6—C5175.03 (18)C12—O1—C11—C10177.8 (2)
C4—C5—C6—C10.3 (4)C9—C10—C11—O2171.0 (3)
C3—C4—C7—C89.2 (4)S2—C10—C11—O29.5 (4)
C5—C4—C7—C8169.9 (2)C9—C10—C11—O17.8 (4)
C3—C4—C7—S2169.0 (2)S2—C10—C11—O1171.65 (17)
C5—C4—C7—S211.9 (3)
Symmetry code: (i) x, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC24H18O4S3
Mr466.56
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)11.8692 (3), 6.0255 (2), 29.7783 (6)
β (°) 94.221 (1)
V3)2123.9 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.48 × 0.44 × 0.18
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.839, 0.935
No. of measured, independent and
observed [I > 2σ(I)] reflections
7327, 2620, 1895
Rint0.062
(sin θ/λ)max1)0.673
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.151, 1.03
No. of reflections2620
No. of parameters142
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.32

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
S1—C11.765 (2)C4—C71.464 (3)
S2—C101.715 (2)C7—C81.364 (3)
S2—C71.718 (2)C8—C91.389 (3)
O1—C121.431 (3)C9—C101.354 (3)
C1—C21.384 (3)C10—C111.462 (3)
C1—S1—C1i103.51 (14)C9—C10—S2111.44 (18)
C10—S2—C791.82 (11)O2—C11—C10124.5 (2)
C6—C1—S1118.83 (17)O1—C11—C10111.4 (2)
C8—C7—S2110.07 (17)
C1i—S1—C1—C6143.3 (2)S2—C10—C11—O29.5 (4)
C1i—S1—C1—C241.89 (19)C9—C10—C11—O17.8 (4)
C5—C4—C7—S211.9 (3)
Symmetry code: (i) x, y, z+3/2.
 

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